CN101190955A - Synthesis technique of acrylic resin for holographic dope - Google Patents
Synthesis technique of acrylic resin for holographic dope Download PDFInfo
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- CN101190955A CN101190955A CNA2007101924026A CN200710192402A CN101190955A CN 101190955 A CN101190955 A CN 101190955A CN A2007101924026 A CNA2007101924026 A CN A2007101924026A CN 200710192402 A CN200710192402 A CN 200710192402A CN 101190955 A CN101190955 A CN 101190955A
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Abstract
The invention discloses a synthesis process of acrylic resin suitable for hologram molding replication coating. According to the influence of monomer ratio, synthesis temperature, polymerization time and type and dosage of evocating agent on the resin property, the process condition of acrylic resin synthesis is that: the mass ratio of methacrylic ester, butyl methacrylate, butyl acrylate, methacrylic acid is 50-70: 20-40: 5: 5; reaction temperature is 120-126 DEG C; reaction time is 0.5-5 hour(s); the dosage of evocating agent is 0.5-1.75 percent of monomer mass; the produced resin solid content is 49.9 percent and viscosity is 5690cP; coating pencil hardness is 1H, glossiness runs up to 90.5Gs. The paper hologram molding replication coating which has good transparency, leveling property, thermal plasticity, brightness, abrasive resistance, water-resistance and acidic and alkali resistance is suitable for being prepared.
Description
Technical field
The present invention relates to a kind of synthesis technique of acrylic resin for holographic dope.
Background technology
A kind of vinylformic acid holographic dope is coated on the paper or the bright smooth coating of the up one-tenth of cardboard of printing-ink, with this memory layer as hologram, on the special soft press of individual cardboard, directly carry out contour forging again, form transparent hologram, the anti-counterfeiting technology of this big area reproducing holographic picture and text is with its powerful anti-counterfeiting power, exquisite decorative effect, simple and direct manufacturing process, lower production cost will be subjected to people's favor (Li Sha, He Hui, Xiong Xianghui. laser embossed holography figure is at anti-counterfeit package Application for Field [J]. Packaging Engineering, 2002,23 (3): 82-84.).
The undertake the printing of characteristic of coating and resin formula of holography directly influences the net result of hologram.Directly die-pressed hologram processing requirement coating has the good transparency on paper product, levelling property, thermoplasticity, luminance brightness, wear resistance, water resisting property, the over-all properties of anti acid alkali performance etc. (referring to: Bao Zuben, Xu Shanjun. the application [J] of antiforge laser holographic technology in plastic composite packaging. Packaging Engineering, 2002,23 (1): 52-54. is referring to CATALINAF, PEINADOC, BLANCO M, et al.Synthesis, photochemical photoinitiationactivity water-soluble copolymer with anthraquinonechromophores as side-chain groups[J] .Polymer, 2001,42:1852-1832.).Realize the above-mentioned characteristic of coating, wherein resin is crucial, and the over-all properties of resin has decisive influence to the holographic effect of coating.
Summary of the invention
Technical problem to be solved by this invention provides a kind of synthesis technique that makes holographic dope have the acrylic resin of the good transparency, levelling property, thermoplasticity, luminance brightness, wear resistance, water resisting property, anti acid alkali performance.
In order to solve the problems of the technologies described above, the synthesis technique of acrylic resin for holographic dope provided by the invention, with methyl methacrylate, butyl methacrylate, butyl acrylate, methacrylic acid compares uniform mixing by certain mass, join in the reactor by formula ratio with initiator then, heated and stirred reaction in reactor behind the feeding rare gas element, reaction finishes back cooling naturally, it is characterized in that: methyl methacrylate: butyl methacrylate: butyl acrylate: it is 50～70: 20～40 that methacrylic acid is formed mass ratio: 5: 5, temperature of reaction is 120-126 ℃, reaction times is 0.5～5 hour, and the consumption of described initiator is 0.5～1.75% of a monomer mass.
Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
Adopt the synthesis technique of the acrylic resin for holographic dope of technique scheme, by acrylate and methacrylic ester and other monomers that contains vinyl group are screened, according to its effect in resin and contribution, select to carry out the quaternary monomer copolymerization with methyl methacrylate (MMA), butyl methacrylate (BMA), butyl acrylate (BA), methacrylic acid (MAA) to filming.Wherein MMA belongs to hard monomer (Tg is 105 ℃), gives coating hardness, wear-resisting, water-fast and transparent BMA hard (Tg is 20 ℃) partially in coating system, and it is good slightly to give the good sticking power of coating, photostabilization and smell, and toxicity is little; BA then belongs to soft monomer (Tg is-54 ℃), gives film flexibility and film-forming properties; The monomeric adding of MAA also has good action to improving polymerization technique, make the synthetic resin have favorable mechanical stability and package stability, it is a hydrophilic monomer, the introducing of polar group, can make to have polar group on the polymer lateral chain, this will increase the sticking power between coating and the base material, and generally selecting consumption is the 3-8% of total monomer amount, cross and to cause multipolymer water tolerance and resistance to abrasion to descend at most, cross and do not reach the ideal effect at least.
By consumption resin property is influenced monomeric proportioning, polymerization temperature, polymerization time and initiator, the optimum process condition of having determined acrylic resin for holographic dope is: methyl methacrylate (MMA): butyl methacrylate (MBA): butyl acrylate (BA): methacrylic acid (MAA) ratio of components is 60: 30: 5: 5, temperature of reaction is 120-126 ℃, reaction times is 5h, and the consumption of initiator Diisopropyl azodicarboxylate is 1.5% of a monomer mass.
Under optimum process condition, the resin solid content of gained is 49.9%, and viscosity is 5690cP, and the pencil hardness of filming is 1H, and glossiness reaches the index that contour forging duplicates coating up to 90.5Gs, is suitable for holograph mould pressing and duplicates coating.
In sum, the present invention is a kind of synthesis technique that makes holographic dope have the acrylic resin of the good transparency, levelling property, thermoplasticity, luminance brightness, wear resistance, water resisting property, anti acid alkali performance.
Description of drawings
Fig. 1 reaction times is to the influence of acid number and iodine number;
The infrared spectrogram of Fig. 2 differential responses time;
The different initiators of Fig. 3 are to the influence of polymer yield.
Embodiment
The performance of filming depends primarily on the monomeric structure of polymer resin.By acrylate and methacrylic ester and other monomers that contains vinyl group are screened, according to its effect in resin and contribution, select to carry out the quaternary monomer copolymerization with methyl methacrylate (MMA), butyl methacrylate (BMA), butyl acrylate (BA), methacrylic acid (MAA) to filming.Wherein MMA belongs to hard monomer (Tg is 105 ℃), gives coating hardness, wear-resisting, water-fast and transparent in coating system; BMA is hard (Tg is 20 ℃) partially, and it is good slightly to give the good sticking power of coating, photostabilization and smell, and toxicity is little; BA then belongs to soft monomer (Tg is-54 ℃), gives film flexibility and film-forming properties; The monomeric adding of MAA also has good action to improving polymerization technique, make the synthetic resin have favorable mechanical stability and package stability, it is a hydrophilic monomer, the introducing of polar group, can make to have polar group on the polymer lateral chain, this will increase the sticking power between coating and the base material, and generally selecting consumption is the 3-8% of total monomer amount, cross and to cause multipolymer water tolerance and resistance to abrasion to descend at most, cross and do not reach the ideal effect at least.
Monomeric ratio finally affects the second-order transition temperature of polymkeric substance and the over-all properties of filming.Table 1 is that different mass is than the influence of monomer to resin and film performance.As can be seen from Table 1, along with the increase of hard monomer ratio, the hardness of resin increases, and viscosity rises under the identical solid content, and second-order transition temperature raises, and this mainly is because the positive fat base of polymethacrylate homologue carbonatoms reduces, due to flexibility reduces.As holographic dope, require can obtain good holographic effect after the mold pressing, second-order transition temperature is low excessively, and coatingsurface is clamminess, the hardness extreme difference, resistance to abrasion extreme difference, hologram are easy to grind off, and the more important thing is that hologram diffraction efficient is low; In addition, the temperature of mold pressing exceeds the softening temperature of coating, just causes " the sticking version " of paper easily, thereby influences the quality [8] of hologram; But second-order transition temperature is too high, and then hardness is excessive, and coating shows as be full of cracks and fragility, is difficult for film forming, has no toughness, and sticking power extreme difference, water-fast, wear-corrosion resistance be extreme difference also.So the vitrifying temperature of resin is advisable for 60-70 ℃.With reference to above measuring result, it is monomeric comparatively more suitable with the D group than row to determine.
Table 1 monomer ratio is to the influence of resin and film performance
| Sample | MMA: BMA: BA: MAA mass ratio | Tg(℃) | Viscosity (cP) (portions of resin solvent=1: 1) | Solid content (%) | Pencil hardness | Sticking power (cross-hatching) | Glossiness (Gs) |
| A B C D | 20∶70∶5∶5 30∶60∶5∶5 50∶40∶5∶5 60∶30∶5∶5 | 34 41.5 58.7 66.1 | 4550 4830 5400 5690 | 50.6 50.1 49.7 49.9 | ＜1B B ＜1H 1H | 0 |
86.2 8 7.7 90.2 90.5 |
| |
70∶20∶5∶5 | 75.2 | 6400 | 49.7 | 2H | 0 grade | 91.4 |
The influence of temperature of reaction
In general, the acrylic resin synthesis temperature generally be controlled in the 70-130 ℃ of scope comparatively suitable.But how to determine the specified temp of a certain reaction, this need determine according to the type of initiator and the boiling temperature of solvent.High spot reviews of the present invention acid number, iodine number, the viscosity change of resin under the different polymerization temperatures, the result is as shown in table 2, as can be seen from Table 2, rising along with temperature of reaction, the acid number of resin and iodine number all reduce gradually, after temperature of reaction rose to 120 ℃, acid number and iodine number then reduced slowly not obvious, illustrated that polyreaction finishes substantially; The viscosity of resin is along with the rising of temperature, increase again after reducing earlier, this is that the free radical that the unit time produces is many more because temperature of reaction is high more, and decomposition of initiator is fast more, the result is when polymerization velocity is accelerated, reduced the polymerization degree, reduced the relative molecular mass of resin, and temperature has been too high, can cause polymkeric substance branching again, the degree of crosslinking increase causes viscosity to rise to some extent.The boiling point of solvent for use N-BUTYL ACETATE is 126 ℃, so final polymerization synthesis temperature is 120～126 ℃.
Table 2 temperature of reaction is to the influence of acid number, iodine number and viscosity
| Temperature of reaction/(℃) | Acid number/(mgg -1) | Iodine number/(mgg -1) | Viscosity/(cP) |
| 80 90 100 110 120 130 | 33.43 31.68 30.42 30.27 29.75 29.78 | 11.61 9.94 9.82 9.46 8.87 8.90 | 6583 6395 6275 5829 5690 6150 |
The influence in reaction times
The polymerization reaction time of the synthesis technique of acrylic resin for holographic dope promptly begins to finish the required time to monomer polymerization reactions from reaction, the results are shown in Figure 1.Along with the growth in reaction times, the acid number and the iodine number of resin descend gradually as seen from Figure 1.And acid number and iodine number all significantly descend in initial one hour, and acid number reduces to 36.68 by 56.735, and iodine number then reduces to 22.6 by 74.5; Acid number and iodine number downward trend tend towards stability in after this three hours, and five hours then constant substantially later on, illustrate that polyreaction five is complete substantially in little.
The present invention also adopts infrared spectra to return polyreaction to follow the trail of, the result as shown in Figure 2, as seen from Figure 2, wave number is 1635.4cm
-1Be unsaturated two strong charateristic avsorption band, carried out one hour when polyreaction that a tangible peak is arranged herein, after three hours, find that two strong absorption peaks obviously reduce, curve tends towards stability when reaction reaches five hours, and the result shows that also polyreaction is complete substantially.
The selection of initiator
In polymerization process, initiator has decisive influence to polymerization velocity.Can think that at a certain temperature rate of polymerization depends mainly on trigger rate.In many cases, rate of polymerization is directly proportional with the initiator concentration square root.The kind of initiator and consumption exert an influence to the viscosity and the transformation efficiency of resin.Initiator commonly used has Diisopropyl azodicarboxylate (AIBN) and benzoyl peroxide (BPO), Fig. 3 is that both are respectively as initiator, polyreaction is descended the polymer yield situation at 120 ℃, in time, the initiation effect of AIBN is better than BPO in same reaction, mainly may be since BPO when resolving into free radical, side reaction has taken place, reduced the concentration of free radical, and there is not the induced decomposition problem in the initiator of azo-type, therefore selects Diisopropyl azodicarboxylate as initiator.Table 3 is to add different amount initiators, the yield of resin and viscosity change, by in the table as can be seen along with initiator amount increases, resin viscosity reduces, this is because being increased in when improving rate of polymerization of initiator concentration reduced the polymerization degree, thereby makes due to the relative molecular weight of resin reduces; Polymer yield is along with the initiator increase is also risen to some extent, but it is little to rise, when initiator amount greater than 1.5% the time, yield almost no longer increases, and determines that therefore the consumption of initiator is 1.5%.
Table 3 initiator amount is to the influence of viscosity and polymerization yield
| Initiator amount/(%) | 0.5 | 0.75 | 1.0 | 1.25 | 1.5 | 1.75 |
| The polymer yield of viscosity/(cP)/(%) | 6533 90.1 | 6025 90.3 | 5862 92.5 | 5734 94.2 | 5690 94.6 | 5310 94.6 |
By consumption resin property is influenced monomeric proportioning, polymerization temperature, polymerization time and initiator, the optimum process condition of having determined acrylic resin for holographic dope is: methyl methacrylate (MMA): butyl methacrylate (MBA): butyl acrylate (BA): methacrylic acid (MAA) ratio of components is 60: 30: 5: 5, temperature of reaction is 120-126 ℃, reaction times is 5h, and the consumption of initiator Diisopropyl azodicarboxylate is 1.5% of a monomer mass.
Under optimum process condition, the resin solid content of gained is 49.9%, and viscosity is 5690cP, and the pencil hardness of filming is 1H, and glossiness reaches the index that contour forging duplicates coating up to 90.5Gs, is suitable for holograph mould pressing and duplicates coating.
Claims (2)
1. the synthesis technique of an acrylic resin for holographic dope, with methyl methacrylate, butyl methacrylate, butyl acrylate, methacrylic acid compares uniform mixing by certain mass, join in the reactor by formula ratio with initiator then, heated and stirred reaction in reactor behind the feeding rare gas element, reaction finishes back cooling naturally, it is characterized in that: methyl methacrylate: butyl methacrylate: butyl acrylate: it is 50～70: 20～40 that methacrylic acid is formed mass ratio: 5: 5, temperature of reaction is 120-126 ℃, reaction times is 0.5～5 hour, and the consumption of described initiator is 0.5～1.75% of a monomer mass.
2. the synthesis technique of acrylic resin for holographic dope according to claim 1, it is characterized in that: described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101706593B (en) * | 2009-11-09 | 2011-08-10 | 中钞特种防伪科技有限公司 | Method for enhancing optical effect of holographic optical element |
| CN102732120A (en) * | 2012-07-20 | 2012-10-17 | 深圳市亿铖达工业有限公司 | Environment-friendly three-proofing paint |
| CN110128876A (en) * | 2019-05-23 | 2019-08-16 | 新乡市新贝尔信息材料有限公司 | A kind of synthetic method for the ink ribbon and its modified polyacrylate resin printing resistance to boiling suitable for infusion bag |
-
2007
- 2007-11-23 CN CNA2007101924026A patent/CN101190955A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101706593B (en) * | 2009-11-09 | 2011-08-10 | 中钞特种防伪科技有限公司 | Method for enhancing optical effect of holographic optical element |
| CN102732120A (en) * | 2012-07-20 | 2012-10-17 | 深圳市亿铖达工业有限公司 | Environment-friendly three-proofing paint |
| CN110128876A (en) * | 2019-05-23 | 2019-08-16 | 新乡市新贝尔信息材料有限公司 | A kind of synthetic method for the ink ribbon and its modified polyacrylate resin printing resistance to boiling suitable for infusion bag |
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Open date: 20080604 |